Index
A
Accumulation in bioreactors, 388
Acetaldehyde
decomposition of, 340
from ethanol, 305
pyrolysis of, 398
Acetic acid, 200
Acetic anhydride production, 537–549
adiabatic operation, 540–541
co-current heat exchange, 542–544
constant heat exchange fluid temperature, 541–542
counter current heat exchange, 544–545
Acetylation reactions, 226
Activation energies
barrier height, 88–89
and bond strength, 92–93
determination, 90–92
in rate laws, 80
and reaction coordinates, 87
Active intermediates, 340–341
chain reactions in, 348
enzymatic reactions, 349
mechanism searches in, 345–348
PSSH in, 341–345
summary, 392–393
Active learners, 683
Active sites
in enzymes, 350
Adenosene diphosphate (ADP), 373
Adenosine triphosphate (ATP), 373
ADH (alcohol dehydrogenase), 366
Adiabatic operations
acetic anhydride production, 540–541
batch reactors, 605–608
butane isomerization, 57–60, 536–537
complex reactions with heat effects, 576–577
CSTRs, 549–554
energy balance, 484–485
batch reactors, 605–608
equilibrium temperature, 504–505
steady-state nonisothermal design, 492–493
tubular reactors, 494
exothermic irreversible gas-phase reactions, 68–69
interstage heat transfer, 505–509
nitroaniline production, 612–613
PFRs, 576–577
propylene glycol production in, 549–554, 605–608
temperature and equilibrium conversion, 502–505
tubular reactors, 493–501
Adsorption, 413
of cumene, 431–437
in CVD, 459–461
dissociative, 270, 422–425, 460
equilibrium constant, 422
isotherms, 420–425
rate constant, 422
in toluene hydrodemethylation, 449–450
Aerobic organism growth, 374
Aerosol reactors, 236–237
Affinity constant in Michaelis–Menten equation, 354
Aiba, S., 378
Air pollution, 28–29
Alcohol dehydrogenase (ADH), 366
Alcohol metabolism, 676
Algae as alternative energy source, 404–405
Algorithms
complex reactions, 308
CRE problems, 142
data analysis, 246–247
ethylene glycol production, 150
vs. memorizing, 140
multiple reactions, 286–288
Aliphatic alcohol, 346
Alkenes, ozone reactions with, 278
Alpha order reactions, 77
Alternative energy, 404–405
Alumina-silica catalyst, 469–470
Amino acids
in chymotrypsin enzyme, 350
synthesis, 373
Ammonia
from hydrogen and nitrogen, 430
nitroaniline from, 608–615
from urea, 361
Ammonolysis, 226
Amylase, 350
Analytical solution for pressure drop, 174, 177–188
Anthracene dimerisation, 101
Antifreeze
from ethylene glycol, 157
from ethylene oxide, 183
Antithrombin, 307
Apparent reactions
in azomethane decomposition, 344
in kinetic rate law, 81
Aqueous bromine, photochemical decay of, 277–278
ARA (attainable region analysis), 326
Area balance in CVD, 459
Arrhenius, Svante, 86
Arrhenius equation, 86–87, 90, 92–93
Arrhenius plots, 90–91
Arrhenius temperature dependence, 362
ARSST, 637
Arterial blood in capillaries, 275
Artificial kidneys, 352
-ase suffix, 349
AspenTech program, 186
acetic anhydride production, 545
explanation of, 670
instructions, 671
Aspirin, 364
Atoms in reactions, 74
Attainable region analysis (ARA), 326
Autocatalytic growth, 67–68
Autocatalytic reactions, 374
Automobile emissions
nitrogen oxides, 278–279, 470–471
in smog formation, 28–29
Azomethane decomposition, 341–345
B
Backmix reactors. See Continuous-stirred tank reactors (CSTRs)
Bacteria, 371–372. See also Cells
in batch reactors, 385–387
in cell growth, 374–376
in enzyme production, 349
Bailey, J. E., 374
Balance on A in semibatch reactors, 229
Balance on heat transfer fluid in tubular reactors, 525–527
Balance on hydrogen in membrane reactors, 219, 222
Basis of calculation in conversions, 34
Batch reactors
adiabatic operation, 605–608
bacteria growth in, 385–387
bioreactors, 384
concentration equations for, 109–111
cylindrical, 136–137
data analysis methods, 248–249
differential, 253–259
integral, 249–253
nonlinear regression, 259–264
design equations for, 34–36, 94
energy balance of, 483, 605–608
enzymatic reaction calculations, 359–361
with interrupted isothermal operation, 608–615
isothermal design, 144–151
mole balances on, 10–12
in design equations, 35
gas phase, 210–212
integral data analysis, 250
runaway, 608–615, 628–630, 640
series reactions in, 298–302
space time in, 61
stoichiometry in, 107–113
Beetles, 101
Benzene
adsorption of, 436
from cumene, 5
in Langmuir–Hinshelwood kinetics, 431–432
in reversible reactions, 83–85
Benzene diazonium chloride, 90–91
Berra, Yogi
on observation, 245
on questions, 26
Berzelius, J., 409–410
Best estimates of parameter values in nonlinear regression, 261
Beta order reactions, 77
Bifurcation problems, 582
Bimolecular reactions, 74
Biochar gasification, 335–336
Bioconversions, 372
Biomass reactions
algae growth, 404–405
in biosynthesis, 372
in nonisothermal reactor design, 643
in reaction rate law, 80
Bioprocessing design problem, 676
Bioreactors, 371–374
autocatalytic growth in, 67–68
cell growth in, 375–376
design equations for, 388–389
mass balances in, 383–387
rate laws in, 376–378
stoichiometry in, 379–383
summary, 392–393
wash-out in, 389–391
Biosynthesis, 372–374
Blanch, H. W., 374
Blindness from methanol, 366
Blood coagulation, 306–307, 327
Blood flows in capillaries, 275
Boltzmann’s constant, 655
Bomb calorimeter reactors, 36
Bond distortions in reaction systems, 88–89
Bonding for enzyme-substrate complex, 350
Boundary conditions, diffusion, 418–419
Briggs–Haldane Equation, 359
Bromine cyanide in methyl bromide production, 230–233
Bulk catalyst density
in packed bed flow, 172
in pressure drop, 180
Burns, Mark, 362
Butadiene from ethanol, 285
Butane
butene from, 221
from cyclobutane, 341
isomerization of, 57–59, 496–501, 530–537
Butanol dehydration, 469–470
Butene from butane, 221
Butyl alcohol (TBA), 468–469
C
Cajun seafood gumbo, 676–677
Calculations
enzymatic reactions, 359–361
propylene glycol production, 552
Calorimeters, 36
Capillaries, arterial blood in, 275
Carbon dioxide from urea, 361
Carbon monoxide
adsorption of, 422–425
methane from, 266–271
Carbonylation reactions in MCMT production, 629
Catalysts and catalytic reactors, 409
adsorption isotherms, 420–425
benzene rate-limiting, 439–440
catalysis, 410–411
classification, 414–415
definitions, 410–411
desorption, 428
for differential reactors, 264–265
diffusion in
from bulk to external transport, 418–419
internal, 419–420
DVD-ROM material, 467–468
in ethylene oxide production, 188
heterogeneous data analysis for, 446–448
mechanisms, 449–450
rate laws, 448–452
reactor design, 453–456
in heterogeneous reactions, 82
membrane reactors, 217–219
in microelectronic fabrication
chemical vapor deposition in, 458–461
overview, 456–458
model discrimination in, 461–464
properties of, 411–412
questions and problems, 468–473
rate laws, 431–434
deducing, 448–449
derived from PSSH, 445
evaluating, 450–452
temperature dependence of, 446
rate-limiting, 428–430, 437–440
reforming, 441–445
steps, 415–430
summary, 465–466
supplementary reading, 475–476
surface reaction, 426–428
weight
ethylene oxide, 183
heterogeneous reactions, 7
membrane reactors, 219
with pressure drop, 178–182
Catalytic dehydration of methanol, 470
CCPS (Center for Chemical Process Safety), 578
Cells
growth and division, 373–376
design equations for, 388–389
and dilution rate, 390
Luedeking–Piret equation, 382
mass balances in, 383–387
stoichiometry in, 379–383
wash-out in, 389–391
reactions in, 372–373
as reactors, 28
Center for Chemical Process Safety (CCPS), 578
Centers in catalysts, 413
Cereals, nutrients in, 238–239
Cerius program, 341
Certificate programs, 579
Chain reactions, 348
Chain transfer step, 348
Channels in microreactors, 212
Characteristic reaction times in batch operation, 146
Chemical reaction engineering (CRE), 1–3
Chemical species, 4–5
Chemical vapor deposition (CVD), 458–461
Chesterton, G. K., 409
Chirping frequency of crickets, 98
Chloral in DDT, 6
Chlorination
membrane reactors, 316
semibatch reactors, 226
Chlorobenzene
from benzene diazonium chloride, 90–91
in DDT, 6
Churchill, Winston, 646
Chymotrypsin enzyme, 350
Clark, D. S., 374
Classes of cell reactions, 373
Clinoptilolite in toluene hydrodemethylation, 446–456
Closed systems, first law of thermodynamics for, 479
Clotting of blood, 306–307, 327
CMRs (catalytic membrane reactors), 217–218
Co-current flow
acetic anhydride production, 542–544
butane isomerization, 533
PFR complex reactions with heat effects, 572–573
in tubular reactors, 525–526
Coagulation of blood, 306–307, 327
Cobalt-molybdenum catalyst, 469
Cobra bites, 328
Cocci growth, 374
Collision rate in adsorption, 422
Collision theory, 78
active intermediates in, 340
Professional Reference Shelf for, 96–97
in reaction systems, 88–89
Combination step
acetic anhydride production, 538
batch operation, 145–146, 299–300
butane isomerization, 496
CSTRs
with cooling coils, 554
series reactions, 303
single, 152–155
ethylene glycol production, 150, 159
ethylene oxide production, 184
gas phase, 211
glucose-to-ethanol fermentation, 386
membrane reactors
flow and reaction in, 223
in multiple reactions, 319
mole balance design, 209
nitroaniline production, 610–611
nitrogen oxide production, 215
nonisothermal reactor design, 478–479
PFR reactor volume, 142–143
pressure drop
isothermal reactor design, 170
tubular reactors, 179
propylene glycol production, 551, 606
tubular reactors
adiabatic, 494
urea decomposition, 360
Combinations
CSTRs and PFRs in, 55–59
and species identity, 5
Competing reactions, 283–284
Competitive inhibition, 364–366
Complex reactions, 308
CSTRs, 311–316
description, 284–285
PBRs, 308–311
PFRs with heat effects, 570–577
Compressibility factors in flow systems, 116
Compression of ultrasonic waves, 346–348
Compression ratio and octane number, 442
COMSOL website with examples, xxiii
program, 670–671
Concentration-time data
in batch reactors, 248
in nonlinear regression, 261–262
Concentrations and concentration profiles
active site balances, 421
batch reactors, 249–250, 300–301
differential reactors, 265–266
dilution, 390
enzyme, 352–353
flow systems, 114
gas-phase, 115–130
key reactants, 118
liquid-phase, 114–115
species, 115–117
methane production, 268–269
with pressure drop, 178
rate data analysis, 246–247
semibatch reactors, 232
toluene hydrodemethylation, 450
Confidence limits in nonlinear regression, 261
Configuration in chemical species, 4
Consecutive reactions, 284
Constant heat capacities in enthalpy, 488
Constant-volume batch systems, 110–111, 253
Constant-volume decomposition of dimethyl ether, 277
Constant volumetric flow for differential reactors, 265
Continuous-flow systems, 113–114
in mole balance, 12–22
reactor time in, 37
sizing, 40–49
Continuous-stirred tank reactors (CSTRs)
in butane isomerization, 501
complex reactions, 311–316
with cooling coils, 554–556
ethylene glycol, 157–162
series, 155–157
single, 152–155
energy balance, 482–483, 547, 554–556, 567–570, 621
in equilibrium equation, 129–130
for ethylene glycol, 147–151
with heat effects, 545–556
for liquid-phase reactions, 12–14
mass balances, 384
multiple reactions, 567–570
with multiple steady states, 556–562
parallel reactions, 159–160, 292–295
propylene glycol production in, 549–554
in series, 50–54
with PFRs, 55–59
sequencing, 59–60
series reactions, 302–306
space time in, 61
for toluene hydrodemethylation, 455–456
unsteady-state operation
energy balance, 483
startup, 620–624
Conversion and reactor sizing, 33–34
batch reactors, 34–36
continuous-flow reactors, 40–49
conversion definition, 34
DVD-ROM material, 65–66
equilibrium. See Equilibrium conversions
flow reactors, 37–40
PBRs, 21
with pressure drop, 178–180
questions and problems, 66–71
rate laws in, 93–94
reactors in series, 49–60
space time, 60–61
space velocity, 62–63
summary, 63–65
supplementary reading, 71
Conversion factors for units, 656–657
Cooking
potatoes, 100
seafood gumbo, 676–677
spaghetti, 196
Coolant balance in tubular reactors, 525–527
Coolant temperature
semibatch reactors, 615–619
steady-state tubular reactors, 526
Cooling coils in CSTRs, 554–556
Coordinates, reaction, 87
Corn starch, 350
Corrosion of high-nickel stainless steel plates, 98–99
Costs in ethylene glycol production, 188–190
Counter current flow
acetic anhydride production, 544–545
butane isomerization, 533–534
PFR complex reactions with heat effects, 574
tubular reactors, 526–527
CRE (chemical reaction engineering), 1–3
Creative thinking, xvii
Cricket chirping frequency, 98
Critical thinking, xvi-xviii
Crystalline aluminosilicates, 411
Crystals in microelectronic fabrication, 457
CSTRs. See Continuous-stirred tank reactors (CSTRs)
Cumene
adsorption, 431–437
in Langmuir–Hinshelwood kinetics, 431–432
Cumene rate law, 439–440
CVD (chemical vapor deposition), 458–461
Cyanide as enzyme inhibitor, 364
Cyclobutane, butane from, 341
Cyclohexanol, 471–472
Cylindrical batch reactors, 136–137
Cytoplasm, 373
Czochralski crystallizers, 457
D
Damköhler numbers in CSTRs
parallel, 160
single, 154–155
Darcy’s Law, 318
Data acquisition for differential reactors, 264
Data analysis. See Rate data collection and analysis
DDT (dichlorodiphenyl-trichloroethane) production, 6
Dean, A. R. C., 378
Death phase in cell growth, 376
Death rate in winemaking, 378
Decomposition in reactions, 5
Dehydration reactions, 469–470
Dehydrogenation reactions, 220–221
Deoxygenation of hemoglobin, 275
Deoxyribonucleic acid (DNA)
identification, 362–364
in protein production, 373
Design and design equations
bioreactors, 388–389
ethylene glycol, 157–162
series, 155–157
single, 152–155
propylene glycol production, 551, 606
toluene hydrodemethylation reactors, 453–455
Desired products
multiple reactions, 285–286
parallel reactions, 289–295
series reactions, 298–306
in toluene hydrodemethylation, 449–450
Diabetes, 402–403
Diameter of tubes in pressure drop, 183
Dichlorodiphenyl-trichloroethane (DDT) production, 6
Diethanolamine formation, 284
Differential forms and equations
Ergun equation, 173
ethylene oxide production, 184
isothermal reactor design, 169
ODE solvers for. See Ordinary differential equation (ODE) solvers
PFR mole balance, 15–16
solutions to, 652–654
triphenyl methyl chloride-methanol reaction, 256–257
tubular flow reactor design equations, 39
Differential reactors, rate data collection and analysis in, 264–271
Differentiation, equal-area graphical, 256–257, 650–651
Diffusion
boundary conditions in, 418–419
from bulk to external transport, 418–419
with catalysts, 418–420
internal, 419–420
Digital-age problems, 322
Dilution rate
in bioreactors, 388–389
in chemostats, 387
in wash-out, 390
Dimerize propylene, 55
Dimethyl ether (DME)
decomposition, 277
from methanol, 470
Diphenyl in reversible reactions, 83–85
Disappearance of substrate, 354–355, 384–385
Disappearance rate, 5–6
Disk rupture in nitroaniline production, 614–615
Dispersion of catalysts, 413
Dissociative adsorption, 270, 422–425, 460
Distortions in reaction systems, 88–89
Division of cells, 373–376
DME (dimethyl ether)
decomposition of, 277
from methanol, 470
DNA (deoxyribonucleic acid)
identification, 362–364
in protein production, 373
Doubling times in growth rates, 378
Drinking and driving, 329
Drug therapy, 364–366
Dual sites
irreversible surface-reaction-limited rate laws in, 445
surface reactions in catalysts, 426–427
DVD-ROM material
active intermediates, enzymatic reactions, pharmacokinetic models, and bioreactors, 393–396
catalysts, 467–468
components, 679–682
conversion and reactor sizing, 65–66
flow reactors with heat exchange, 581–582
isothermal reactor design, 192–194
for learning styles, 683–684
molar flow rates, 235–237
mole balances, 24–26
multiple reactions, 325–326
navigating, 682–683
nonisothermal reactor design
steady-state, 512–513
unsteady-state, 637–638
open-ended problems, 675–677
rate data collection and analysis, 273–274
rate laws, 96–97
stoichiometry, 132–133
E
Eadie–Hofstee plots, 357–358
Economic decisions and incentives for separations systems, 285
Efficient parallel reactor schemes, 289
Electronics industry, microelectronic fabrication, 279
chemical vapor deposition in, 458–461
overview, 457–458
Elementary rate laws, 76–79
Eley–Rideal mechanism, 441
irreversible surface-reaction-limited rate laws, 445
in surface reactions in catalysts, 427–428
Emissions, automobile
nitrogen oxides in, 278–279, 470–471
in smog formation, 28–29
Endothelium in blood clotting, 306
Endothermic reactions
equilibrium conversion in, 502
interstage heat transfer, 506–507
Energy
alternative, 404–405
conversion factors, 656
Energy balances
acetic anhydride production, 538
adiabatic operations, 484–485
batch reactors, 605–608
equilibrium temperature, 504–505
in steady-state nonisothermal design, 492–493
tubular reactors, 494
butane isomerization, 497, 532
CSTRs, 482–483
with cooling coils, 554–556
heat exchanger in, 547
in multiple reactions, 567–570
unsteady-state operation, 621
ethyl acetate saponification, 618
first law of thermodynamics, 479–480
heat of reaction in, 489–492
MCMT production, 632–633
nitroaniline production, 611
overview of, 482–485
PFRs, 483
with heat effects, 528–529
with heat exchange, 522–525
multiple reactions, 563–570
parallel reactions, 565
propylene glycol production, 552, 606, 621
semibatch reactors, 483
with heat exchangers, 616
multiple reactions, 626–627
steady-state molar flow rates, 486–488
tubular reactors, 522–525
unsteady-state nonisothermal reactors, 602–604
work term in, 480–482
Energy barriers, 87–88
Energy distribution function, 89
Energy economy
hydrogen-based, 240
membrane reactors, 220–221
Energy rate change with time, 657
Engine knock, 441–443
Engine oil, 398–399
Engineering experiment design problem, 675
Entering concentrations in flow reactor design, 37
Enthalpies in energy balance, 481, 488–489
Enzymatic reactions, 80, 349–350
batch reactor calculations for, 359–361
Briggs–Haldane Equation, 359
Eadie–Hofstee plots, 358
enzyme-substrate complex, 350–351
induced fit model, 351
inhibition of. See Inhibition of enzyme reactions
lock and key model, 351
mechanisms, 352–354
Michaelis–Menten equation, 354–359
summary, 392–393
temperature in, 362
Enzyme-catalyzed polymerization of nucleotides, 362–364
Enzyme Man, 394
Epidemiology, PSSH for, 399–400
Epitaxial germanium, 458–459
Epoxydation of ethylene, 333–334
Equal-area differentiation, 256–257, 650–651
Equations
batch concentrations, 109–111
concentrations in flow systems, 114
differential. See Differential forms and equations
Equilibrium
in adiabatic equilibrium temperature, 503
in CVD, 461
Equilibrium constant
in adiabatic equilibrium temperature, 504
in thermodynamic relationships, 659–664
Equilibrium conversions, 502
and adiabatic temperature, 502–505
butane isomerization, 498
endothermic reactions, 502, 506–507
exothermic reactions, 502–505
feed temperature, 509–511
semibatch reactors, 233
with variable volumetric flow rate, 125–130
Ertl, Gerhard, 410
Esterification reactions, 226
Etching, semiconductor, 279
Ethane
from azomethane, 341–345
ethylene from, 469
in ethylene glycol production, 189–190
ethylene hydrogenation to, 462–464
Ethanol
acetaldehyde from, 305
ADH with, 366
butadiene from, 285
in glucose-to-ethanol fermentation, 385–387
in wine-making, 377
pharmacokinetic metabolism, 329, 395
Ethoxylation reactions, 316
Ethyl acetate saponification, 616–619
Ethylbenzene, styrene from, 220–221
Ethylene
adsorption of, 413–414
epoxydation of, 333–334
from ethane, 469
ethane from, 462–464
PBRs for, 165–168
Ethylene chlorohydrin, 239
Ethylene glycol (EG)
CSTRs for, 147–151
from ethylene chlorohydrin and sodium bicarbonate, 239
from ethylene oxide, 183
production of, 157–162
synthesizing chemical plant design for, 188–190
Ethylene oxide, 284
in ethylene glycol production, 188
production of, 183–188
Eukaryotes, doubling times for, 378
Evaluation
batch operations, 145–146, 301–302
CSTR series reactions, 304–305
ethylene glycol production, 150, 159
gas phase, 210
nitrogen oxide production, 215
PFR reactor volume, 142–143
propylene glycol production, 607, 620–621
toluene hydrodemethylation, 456
triphenyl methyl chloride-methanol reaction, 256
tubular reactor design, 167–168
Excel
for activation energy, 90–92
for trityl-methanol reaction, 252–253
Excess method in batch reactors, 248
Exhaust streams, automobile
nitrogen oxides in, 278–279, 470–471
in smog formation, 28–29
Exit points in CSTRs, 13
Exit temperature in interstage cooling, 507
Exothermic reactions, 491, 502
equilibrium conversion in, 502–505
interstage heat transfer, 505–509
safety issues, 577–579, 608–615
Experimental observation, 8, 78
Experimental planning
Professional Reference Shelf for, 274
in rate data collection and analysis, 271
Explosions
Monsanto plant, 608–615
nitrous oxide plant, 585–586, 641
Explosive intermediates, microreactors for, 212
Exponential cell growth, 376–377
External diffusion effects. See Diffusion
Extinction temperature in multiple steady states, 561
Eyes, blindness from methanol, 366
F
Fabrication, microelectronic, 279
chemical vapor deposition in, 458–461
overview, 456–458
Factor novoseven, 307
Fanning friction factor, 175
Fast orange formation, 135
FAQs, xxiii
Fed batch reactors. See Semibatch reactors
Feed temperature in equilibrium conversion, 509–511
Femtosecond spectroscopy, 341
Fermentation
glucose-to-ethanol, 385–387
in wine-making, 377–378
Fermi, Enrico, 30
Fibers, terephthalic acid for, 331
Fibrin, 306
Fibrinogen, 306
Firefly flashing frequency, 98
First law of thermodynamics, 479–480
First-order dependence in CFRs, 40
First-order ODE solutions, 652
First-order rate laws, 79
First-order reactions, 77
batch operations, 146
CSTR design
series, 155–156
single, 152–153
differential equations for, 652
multiple steady states, 559
PFR reactor volume for, 142–144
reversible, 502
Five-point quadrature formula
in PFR sizing, 46
solutions, 653–654
Fixed-bed reactors. See Packed-bed reactors (PBRs)
Flame retardants, 397
Flashing frequency of fireflies, 98
Flow
in energy balance, 480
through packed beds, 170–174
in pipes, pressure drop in, 174–177
Flow rates
molar. See Molar flow rates
multiple reactions, 286
space time, 61
Flow reactors, 113–114. See also specific flow reactors by name
concentrations in, 114
gas-phase, 115–130
liquid-phase, 114–115
design equations, 37–40
CSTR, 38
PBRs, 39–40
tubular, 38–39
with heat exchange, 521
balance on transfer fluid, 525–527
CSTRs, 545–556
DVD-ROM material, 581–582
multiple steady states, 556–563
nonisothermal reactions, 563–577
PFR/PBR design algorithm, 527–545
questions and problems, 583–598
safety, 577–579
steady-state tubular reactors, 522–525
summary, 579–580
supplementary reading, 598–599
with variable volumetric flow rate, 115–130
Fluidized-bed reactors, 83
Fluidized continuous-stirred tank reactors, 455–456
Force, conversion factors for, 656
Formaldehyde
from methanol, 366
oxidation of, 333
Formate from methanol, 366
Formation enthalpies, 488–489
Formation rates in azomethane decomposition, 342
Four-point rule in integral evaluation, 653
Fractional area balance in CVD, 459
Free radicals
as active intermediates, 340
in bimolecular reactions, 74
Frequency factors in activation energy, 91
Freudlich isotherms, 425
Friction factor in pipe pressure drop, 175
Fuel cells, 240
Furusawa, T., 550
G
Gallium arsenide layers, 458
Gas-hourly space velocity, 62
Gas phase and gas-phase reactions
adiabatic exothermic irreversible, 68–69
complex reactions with heat effects in PFRs, 571
in CVD, 459
dimethyl ether decomposition, 277
elementary and reversible, 83
equilibrium constant in, 659–661
flow reactors, 37–38, 116, 120–123
liquid-phase concentrations, 115
microreactors, 213–217
mole balances on, 210–212
mole changes in, 115–130
packed beds, 140
PBRs, 308–311
PFR reactor volume, 142–144
pressure drop in, 169–170
tubular reactors, 14, 163–165, 524
Gas-solid heterogeneous reactions, 246
Gas volumetric flow rate in space velocity, 62
Gasoline octane number, 506–507
Gaussian program, 341
General mole balance equation, 8–10
for CSTRs, 13
for tubular reactors, 15
Generation heat in multiple steady states, 558–560
Generic power law rate laws in gas phase, 210
Germanium epitaxial film, 458–459
GHSV space velocity, 62
Gibbs free energy
in cumene adsorption, 435
in equilibrium constant, 661–662
Global learners, 683
Glow sticks, 348
Glucose in wine-making, 377
Glucose-to-ethanol fermentation, 385–387
Goodness of fit in rate data analysis, 247
Gradientless differential reactors, 265
Graphical methods
batch reactor data analysis, 254
equal-area differentiation, 650–651
triphenyl methyl chloride-methanol reaction, 256–258
Gravitational conversion factor, 657
Greek symbols, 667
Green engineering, xxiii, 406
Growth of microorganisms. See Bioreactors
Gumbo, 676–677
H
Hanes–Woolf model
for Michaelis–Menten equation, 357–358
of Monod equation, 383
Heat capacities in enthalpy, 488
Heat effects. See also Temperature
CSTRs with, 545–556
in semibatch reactors, 616–619
in steady-state nonisothermal reactors. See Steady-state nonisothermal reactors
Heat exchange in steady-state nonisothermal reactors. See Flow reactors
Heat exchangers
acetic anhydride production, 541–543
energy balance in, 547
in interstage cooling, 508
in microreactors, 212
PFR/PBR with heat effects, 529
in semibatch reactors, 615–619
Heat load in interstage cooling, 508
Heat of reactions
in energy balance, 489–492
molar flow rates for, 486–488
Heat terms in multiple steady states, 557–560
Heat transfer
to CSTRs, 547
in octane number, 506–507
in pressure drop, 183
in tubular reactors, 525–527
Height, energy barrier, 88
Hemoglobin, deoxygenation of, 275
Hemostatis process, 306
Heptane, 441–442
Heterogeneous catalytic processes
in methane production, 269
phases in, 410–411
Heterogeneous data analysis, 446–448
mechanisms, 449–450
rate laws, 448–452
reactor design, 453–456
Heterogeneous reactions, 7, 74, 82–83
data for, 246
external diffusion effects on. See Diffusion
High-fructose corn syrup (HFCS), 350
High-nickel stainless steel plates, 98–99
High temperature in multiple steady states, 559
Holding time in space time, 61
Homogeneous reactions, 74, 80–82
catalytic, 410–411
data for, 246
rate law parameters for, 248
Hot spots in microreactors, 212
Hougen, O. A., 429
Humphrey, A. E., 378
Hydrocarbons, partial oxidation of, 316
Hydrodemethylation of toluene, 82, 446–456
Hydrodesulfurization reactor design problem, 676
Hydrogen
ammonia from, 430
dissociative adsorption of, 460
in enzyme-substrate complex, 350
in membrane reactors, 219
in methane production, 266–271
in reversible reactions, 83–85
from water-gas shift reaction, 662–663
water splitting, 472–473
Hydrogen-based energy economy, 240
Hydrogen peroxide
decomposition, 400
sodium thiosulfate reaction, 556
Hydrogenation reactions
of ethylene to ethane, 462–464
membrane reactors for, 316
Hydrolases enzymes, 351
Hydrolysis
in semibatch reactor operation, 226
of starch, 401–402
Hydrophobic forces for enzyme-substrate complex, 350
I
Ideal gas constant, 655
Ideal gas law, 37
Identity
in chemical species, 4
in reactions, 5
Ignition-extinction curves, 560–563
Ignition temperature
in equilibrium conversion, 510
in multiple steady states, 561
IMRCFs (inert membrane reactors with catalyst pellets on the feed side), 217–218
Independent reactions, 284, 563
Induced fit model for enzyme-substrate complex, 351
Industrial reactors
dimerize propylene into isohexanes, 55
in mole balance, 22–23
space time in, 61
visual encyclopedia of equipment, xxiii
Industrial waste reaction, 204
Inert membrane reactors with catalyst pellets on the feed side (IMRCFs), 217–218
Inhibition of enzyme reactions, 364
competitive, 364–366
noncompetitive, 368–370
substrate, 370–371
uncompetitive, 367–368
Inhibitor molecules, 368
Inhibitors, 364
Initial rates for differential reactors, 264
Initiation step in chain reactions, 348
Inlet conditions
differential reactors, 266
equilibrium conversion, 510–511
Instantaneous selectivity
multiple reactions, 285–286
semibatch reactors, 227
Instantaneous yield in multiple reactions, 286
Insulin
Januvia for, 402–403
production, 372
Integral data analysis method, 249–253
Integrals
numerical evaluation, 652–654
in reactor design, 649–650
Integrated circuit fabrication
CVD in, 458–461
overview, 456–458
Interfacial area for catalytic reactions, 411
Intermediates, active. See Active intermediates
Internal diffusion, 419–420
Interrupted isothermal operations, 608–615
Interstage heating and heat transfer
reactor staging with, 505–509
reactor trains with, 518
Intuitive learners, 684
Ionic forces for enzyme-substrate complex, 350
Irreversible reactions, 74
endothermic, 515–516
exothermic, 68–69
isomerization, 446
order in, 248
Irreversible surface-reaction-limited rate laws, 445
Iso-octane, 441–443
Isobutane production, 496–501, 530–537
Isohexanes from dimerize propylene, 55
Isomerases enzymes, 351
Isomerization
batch reactors, 11–12
butane, 57–60, 496–501, 530–537
irreversible, 446
isothermal gas-phase, 41
in reactions, 5
Isopropyl isocyanate decomposition, 279–280
Isotherm equation in adsorption, 425
Isothermal operations
flow reactors, 121
gas-phase isomerization, 41
interrupted, 608–615
nitroaniline production, 611–612
sulfur dioxide gas-phase reactions, 121
sulfur dioxide rate law, 123
Isothermal reactors, 139
batch, 144–151
CSTRs, 152
design equations, 94
ethylene glycol, 157–162
series, 155–157
single, 152–155
DVD-ROM material, 192–194
learning resources for, 192–193
molar flow rates. See Molar flow rates
ODE solver algorithm, 192
pressure drop, 169
analytical solution, 177–188
flow through packed beds, 170–174
in pipes, 174–177
rate law, 169–170
questions and problems, 194–206
structure for, 140–144
summary, 191
supplementary reading, 206
synthesizing chemical plant design, 188–190
tubular reactors, 162–168
Isotherms, adsorption, 420–425
J
Jeffreys, G. V., 537
Johnson, Samuel, 339
K
Kargi, F., 373–374
Key reactant concentrations, 118
Kidneys, artificial, 352
Kind in chemical species, 4
Kinetic Challenge module, 133
Kinetic energy in energy balance, 481
L
Labs-on-a-chip
for DNA identification, 362–364
microreactors for, 212
Lag phase in cell growth, 375
Langmuir, Irving, 423
Langmuir–Hinshelwood kinetics
in catalyst surface reactions, 427
for heterogeneous reactions, 82, 246
nonlinear regression for, 259
in rate limiting, 429
steps in, 431–432
Langmuir isotherm, 423–425
Large molecules, synthesis of, 373
Le Chatelier’s principle, 661
Learning resources, xx, 24, 65, 94, 130, 192, 235, 273, 325, 393, 467, 512, 581, 637, 679
active intermediates, enzymatic reactions, pharmacokinetic models, and bioreactors, 393–394
catalysts, 467
conversion and reactor sizing, 65
explanation of, 679–680
flow reactors with heat exchange, 581
isothermal reactor design, 192–193
molar flow rates, 235–236
mole balances, 24–25
multiple reactions, 325
nonisothermal reactor design
steady-state, 512
unsteady-state, 637
rate data collection and analysis, 273
rate laws, 96
stoichiometry, 132–133
Learning styles, 683–684
Least-squares analysis
batch reactors, 259
multiple reaction analysis, 321
Professional Reference Shelf for, 273–274
LeBlanc, Steve, 601
Length conversion factors, 656
Levenspiel plots
adiabatic isomerization, 59
butane isomerization, 499
PFRs in series, 54
LHSV space velocity, 62
Ligases enzymes, 351
Light from ultrasonic waves, 346–348
Limiting reactants
in batch systems, 112–113
in conversion, 34
Lindermann, F. A., 340
Linear least squares, 259
Linear plots in batch reactor data analysis, 249–251
Lineweaver–Burk plots
for inhibition
competitive, 366
noncompetitive, 369
uncompetitive, 368
for Michaelis–Menten equation, 356–357
Liquid-hourly space velocity, 62
Liquid phase and liquid-phase reactions
batch systems, 36, 110–111, 144
butane isomerization, 57–60, 496–501
complex reactions, 312–314
concentrations, 114–115
MCMT production, 628
methanol-triphenyl reaction, 277
pressure drop, 169
selectivity in, 226–227
semibatch reactors, 314–316
Living example problems, xxii, 131, 193, 236, 273, 325, 394, 467, 512, 582, 637, 680
active intermediates, enzymatic reactions, pharmacokinetic models, and bioreactors, 394
catalysts, 467
explanation, 680
flow reactors with heat exchange, 582
isothermal reactors, 193
molar flow rates, 236
multiple reactions, 325–326
nonisothermal reactors
steady-state, 512
unsteady-state, 637
rate data collection and analysis, 273
Locally stable steady-state values, 562
Lock and key model, 351
Log-log paper
for batch reactor analysis, 253–254
for triphenyl methyl chloride-methanol reaction, 257
Logic vs. memorizing, 140, 142
Logistic growth law, 403
London van der Waals forces, 350
Los Angeles basin, 28–29
Low temperature in multiple steady states, 559
Lubricant design problem, 675
Luedeking–Piret equation, 382
Luminescence from ultrasonic waves, 346–348
Lyases enzymes, 351
M
Maintenance in cell growth, 380
Marx, Groucho, 139
Mass balances. See also Mole balances
in cell growth, 383–387
in glucose-to-ethanol fermentation, 385–386
Mass conversion factors, 656
Mass flow rate through packed beds, 171
Mass transfers in microreactors, 212
Material Safety Data Sheets (MSDS), 162
MATLAB program
adiabatic tubular reactors, 493
ethylene oxide production, 186
instructions, 671
isothermal reactors, 192
membrane reactors, 223–224
non-adiabatic PFR energy balance, 485
nonlinear regression, 261
MCMT (methylcyclopentadienyl manganese tricarbonyl) production, 628–635
Mean residence time in space time, 61
Measured variables
in rate data analysis, 246
in triphenyl methyl chloride-methanol reaction, 255
Mechanism searches, 345–348
Medical applications. See Pharmacokinetics
MEK (methyl ethyl ketone) production, 471
Membrane reactors
design, 217–225
mole balances, 208–209
for multiple reactions, 316–321
packed bed, 172
Memorization vs. logic, 140, 142
Metabolism of alcohol, 676
Metaxylene isomerization, 200
Methane
from carbon monoxide and hydrogen, 266–271
para-xylene from, 411
Methanol
ADH with, 366
dimethyl ether from, 470
synthesis problem, 676
in triphenyl methyl chloride reaction, 255–259
in trityl-methanol reaction, 251–253
Methanol-triphenyl reaction, 277
Methyl amine, 230–233
Methyl bromide production, 230–233
Methyl ethyl ketone (MEK) production, 471
Methylcyclohexane, toluene from, 474
Methylcyclopentadienyl manganese tricarbonyl (MCMT) production, 628–635
Michaelis constant, 354–355, 366
Michaelis–Menten kinetics and equations
in competitive inhibition, 364–366
in enzymatic reactions, 354–359
substrate concentration in, 360
in uncompetitive inhibition, 367–368
Microbial growth. See Bioreactors
Microelectronic fabrication, 279
chemical vapor deposition in, 458–461
overview, 456–458
Microfluids in DNA identification, 362–364
Microorganism growth. See Bioreactors
Microreactors
molar flow rate algorithm, 212–217
for phosgene, 202–203
Mild reaction conditions in bioconversions, 372
Mills, N. F., 378
Mixed inhibition, 368–370
Mixers in microreactors, 212
Miyauchi, T., 550
Model discrimination in catalysts, 461–464
Molar feed rate in flow reactors, 37
Molar flow, 114
CSTRs, 14
ethylene glycol production, 188
flow reactors, 37, 115–117, 127
gas phase, 210
heat of reaction, 486–488
membrane reactors, 317–318
multiple reactions, 286, 317–318, 320
PFR/PBR with heat effects, 528
PFRs, 16–17
Molar flow rates, 207
balance equation, 208
DVD-ROM material, 235–237
learning resources, 235–236
membrane reactors, 217–225
microreactors, 212–217
mole balances, 208–212
ODE solver algorithm, 235
questions and problems, 237–243
semibatch reactors, 226–233
summary, 233–234
supplementary reading, 243
unsteady-state operation of stirred reactors, 225–226
Mole balances, 1–4
acetic anhydride production, 538–539
adiabatic tubular reactors, 494
batch reactors, 10–12, 144–146
in design equations, 35
enzymatic reactions, 359
integral data analysis, 250
series reactions, 299–300
butane isomerization, 496, 531
CFRs, 12–22
CSTRs, 38
with cooling coils, 554
liquid phase, 312
multiple reactions, 568
unsteady-state operation, 621
DVD-ROM material, 24–26
ethyl acetate saponification, 617
ethylene glycol production, 148–149, 158
general mole balance equation, 8–10
industrial reactors, 22–23
learning resources for, 24–25
liquid phase, 208, 210, 312, 314
MCMT production, 631–632
membrane reactors, 219, 221–222, 318
multiple reactions, 286–287, 318, 568, 626
nitroaniline production, 610
nitrogen oxide production, 214
nonisothermal reactor design
steady-state, 478
unsteady-state, 603
PBRs, 18–19, 208–212, 308, 528
PFRs
first-order gas-phase reaction, 142–143
Professional Reference Shelf for, 25–26
propylene glycol production, 551, 621
questions and problems for, 26–31
rate data analysis, 246
reaction rate, 4–8
semibatch reactors, 227–228, 230, 314, 626
summary, 23–24
supplementary reading, 31
toluene hydrodemethylation, 456
triphenyl methyl chloride-methanol reaction, 255
tubular reactors, 39
adiabatic, 494
design, 166
with heat exchange, 524
Molecular adsorption, 422–423
Molecular dynamics, 97
Molecular sieves, 411
Molecularity of reactions, 74
Moles
in batch systems, 107–109
in reactors in series, 49
Monod equation
for exponential growth, 376–377
Hanes–Woolf form of, 383
Monoethanolamine formation, 284
Monolithic catalysts, 411
Monsanto plant accident, 608–615
Moser growth law, 378
MOSFET devices, 457
Motor oil, 398–399
MSDS (Material Safety Data Sheets), 162
Multiple reactions, 283
algorithms, 286–288
analysis for, 321
complex. See Complex reactions
for digital-age problems, 322
DVD-ROM material, 325–326
membrane reactors for, 316–321
nonisothermal, 563
energy balance in, 563–570
unsteady-state, 624–635
in packed bed flow, 172
parallel. See Parallel reactions
in PBRs, 308–311
questions and problems, 326–337
series, 283–284
batch reactors, 298–302
in blood clotting, 306–307
CSTR, 302–306
summary, 323–324
supplementary reading for, 337–338
types, 283–286
Multiple regression techniques, 451–452
Multiple steady states, 556–557
heat of generation in, 558–560
heat-removed terms, 557–558
ignition-extinction curves, 560–563
Multiple substrate systems, 395
Multiplication, cell, 374
Mystery Theater module, 196
N
N-butyl alcohol, dehydration of, 469–470
National Oceanic and Atmosphere Administration (NOAA), 578
Navigating DVD-ROM, 682–684
Neoplastic diseases, 364
Net rates
batch reactor series reactions, 300
CSTRs
liquid phase, 312
series reactions, 303
MCMT production, 632
membrane reactors, 318
PBR gas phase reactions, 309
PFR complex reactions with heat effects, 571
Nickel catalysts, 266–271
Nicotine species, 4
Nishimura, H., 550
Nitration reactions, 316
Nitroaniline from ammonia and ONCB, 579, 609–610
adiabatic operation, 612–613
batch operation with heat exchange, 613–614
disk rupture in, 614–615
isothermal operation, 611–612
Nitrogen
ammonia from, 430
from azomethane, 341–345
from benzene diazonium chloride, 90–91
Nitrogen dioxide
from nitrogen oxide, 398
from reversible gas-phase decompositions, 125–130
Nitrogen oxides
in automobile emissions, 278–279, 470–471
nitrogen dioxide from, 398
production of, 213–217
Nitrogen tetroxide decomposition, 125–130
Nitrous oxides in plant explosion, 585–586, 641
NOAA (National Oceanic and Atmosphere Administration), 578
Nomenclature, 665–667
Non-adiabatic energy balance, 485
Non-enzymatic lipoprotein, 306
Noncompetitive inhibition, 368–370
Nondissociated adsorption, 422
Nonelementary rate laws, 80–83, 340–341
chain reactions in, 348
mechanism searches in, 345–348
PSSH in, 341–345
summary, 392–393
Nongrowth associated product formation, 379, 381
Nonisothermal reactions, 563
steady-state. See Steady-state nonisothermal reactors
unsteady-state. See Unsteady-state nonisothermal reactors
Nonlinear least-squares, 321
Nonlinear regression
batch reactor data analysis, 259–264
cell growth, 383
ethylene hydrogenation to ethane, 462–463
Michaelis–Menten equation, 359
Norbornadiene–Quadricyclane couple, 102
Normal pentane, octane number of, 443
Nuclear processes, Fermi work on, 30
Nuclear reactor problem, 675
Nuclear region in cells, 373
Nucleotides, polymerization of, 362–364
Number in chemical species, 4
Numerical techniques
adiabatic tubular reactors, 495
differential equations. See Differential forms and equations
equal-area graphical differentiation, 650–651
integrals
numerical evaluation of, 652–654
in reactor design, 649–650
MCMT production, 633
for membrane reactors, 223
Nutrients
cell growth, 380–381
ready-to-eat cereals, 238–239
O
Octane, butyl alcohol for, 468–469
Octane number
interstage heat transfer in, 506–507
in petroleum refining, 441–443
ODE. See Ordinary differential equation (ODE) solvers
Oil, engine, 398–399
Ollis, D. F., 374
ONCB
nitroaniline from, 609–610
orthonitroaniline from, 135
One-third rule, 653
Open-ended problems, 675–677
Open systems, first law of thermodynamics for, 479
Operating conditions in parallel reactions, 295–298
Operating costs in ethylene glycol production, 188–190
Optimum feed temperature in equilibrium conversion, 509–511
Optimum yield in batch reactor series reactions, 301
Orbital distortions, 89
Order, reaction, 76–86
Order of magnitude of time in batch operation, 146
Ordinary differential equation (ODE) solvers. See also MATLAB program; Polymath program
adiabatic tubular reactors, 495
gas phase, 211
isothermal reactors, 192
molar flow rates, 235
multiple reactions, 322
Organic reactions, liquid-phase, 110
Orthonitroaniline from ammonia and ONCB, 135
Oscillating reactions, 327
Ostwald, Wilhelm, 410
Other work term in energy balance, 480
Overall mass balance, 228
Overall mass transfer coefficient, 220
Overall selectivity
membrane reactors, 317
multiple reactions, 285–286, 317
Overall yield in multiple reactions, 286
Oxidation
of formaldehyde, 333
membrane reactors for, 316
Oxidation problem, 675
Oxidoreductases enzymes, 351
Oxygen in water splitting, 472–473
Ozone reactions with alkenes, 278
P
Packed-bed reactors (PBRs), 12, 18–22
adiabatic, 493–500
complex reactions, 308–311
design equations for, 94
energy balance for, 483
flow reactor design equations, 39–40
gas-phase reactions, 140
with heat exchange, 483
acetic anhydride production, 537–545
algorithm, 527–530
butane isomerization, 530–537
ODE solvers algorithms for, 192
pressure drop, 170–177
for toluene hydrodemethylation, 453–455
Para-xylene, 411
Parallel reactions, 283–284
desired products in, 289–295
PFRs with heat effects, 564–567
reactor selection and operating conditions in, 295–298
Parameters
butane isomerization, 497–498
ethylene oxide production, 185
membrane reactors, 223
nonlinear regression, 261
propylene glycol production, 607, 620–621
toluene hydrodemethylation, 450–452
tubular reactor design, 167–168
Partial oxidation, membrane reactors for, 316
Partial pressures
profiles, 454–455
in sulfur dioxide rate law, 123–125
Particle size
in internal diffusion, 419–420
in pressure drop, 181–182
PBRs. See Packed-bed reactors (PBRs)
Peach Bottom nuclear reactor problem, 675
Pellets in internal diffusion, 419
Penicillium chrysogenum
formation, 376
as reactors, 28
Peptides, 402
Perfect mixing in CSTRs, 13, 38, 290
PFRs. See Plug-flow reactors (PFRs)
Pharmacokinetics
competitive inhibition, 364–366
in drinking and driving, 329
summary, 392–393
Tarzlon, 329–330
Phases
cell growth, 375
enthalpy, 488
gas. See Gas phase and gas-phase reactions
heterogeneous reactions, 7
liquid. See Liquid phase and liquid-phase reactions
Phosgene production, 202–203
Photochemical decay of aqueous bromine, 277–278
Photoresist, 279
Photos of real reactors, 25
Phthalic anhydride, 1–2
Physical adsorption, 413
Picasso’s reactor, 17
Pipes, pressure drop in, 174–177
Platinum on alumina as reforming catalyst, 442–444
Plug flow in tubular reactor design, 163, 166
Plug-flow reactors (PFRs), 12, 14–18
adiabatic, 493–501
butane isomerization, 498–500
complex reactions with heat effects, 570–577
CSTRs in series as approximation of, 53–59
design equations for, 38–39
energy balance, 483
with heat exchange, 522–525
multiple reactions, 563–564
parallel reactions, 565
ethylene production in, 165–168
for gas-phase reactions, 142–144
with heat exchange, 527–530
acetic anhydride production, 537–545
butane isomerization, 530–537
mole balances on, 208–212
multiple reactions, 563–564
parallel reactions, 293–295, 564–567
reactor volume for, 142–144
runaway in, 582
in series, 54
with CSTRs, 55–59
sequencing, 59–60
series reactions, 305–306
sizing, 45–49
Point of no return in nitroaniline production, 613
Polanyi–Semenov equation, 92
Polished wafers in microelectronic fabrication, 457
Polyesters
ethylene glycol for, 157
from ethylene oxide, 183
Polymath program
acetic anhydride production, 540–545
blood clotting, 307
butane isomerization, 499–500, 532, 534–535
cell growth, 383
CSTRs
with cooling coils, 555
liquid phase, 313
with multiple reactions, 569–570
unsteady-state operation, 622–623
energy balance, 485
ethyl acetate saponification, 618–619
ethylene hydrogenation to ethane, 462–463
ethylene oxide production, 186–188
explanation, 669–670
glucose-to-ethanol fermentation, 386
heat effects, 566
instructions, 671
isothermal reactors, 192
MCMT production, 633–635
membrane reactors, 223–224, 319
methane production, 270–271
methyl bromide production, 231–232
Michaelis–Menten equation, 359
multiple reactions, 319, 569–570, 627
nitroaniline production, 613
nitrogen oxide production, 215–216
nonlinear regression, 261–263, 383
PBR gas phase reactions, 310–311
propylene glycol production, 553–554, 607–608, 622–623
semibatch reactors, 627
toluene hydrodemethylation, 451–452, 454
trityl-methanol reaction, 252–253
tubular reactors, 493
variable volumetric flow rate, 127–128
Polymerization, 395
in bioreactors, 373
nucleotides, 362–364
Professional Reference Shelf for, 394–395
Polymers production, 372
Porous catalyst systems, 411
Potatoes, cooking, 100
Potential energy in energy balance, 481
Power law
and elementary rate laws, 76–79
in gas phase, 210
for homogeneous reactions, 246
Practical stability rate
in CSTR unsteady-state operation, 620
in propylene glycol production, 623
Pressure
conversion factors, 656
in energy balance, 480
in flow reactors with variable volumetric flow rate, 116
in sulfur dioxide rate law, 123–125
Pressure drop
in ethylene oxide production, 183–188
in isothermal reactor design, 169, 209
analytical solution for, 177–188
flow through packed beds, 170–174
in pipes, 174–177
rate law in, 169–170
tubular reactors with heat exchange, 524
Pressure profiles, 454–455
Price in ethylene glycol production, 188–190
Product-enzyme complex, 359
Product formation in cell growth, 379–383
Production rate in dilution, 390
Professional Reference Shelf, xxii, 25, 66, 94, 193, 236, 273, 326, 394, 467, 513, 582, 637, 680
active intermediates, enzymatic reactions, pharmacokinetic models, and bioreactors, 394–396
catalysts, 467–468
conversion and reactor sizing, 66
explanation of, 680
flow reactors with heat exchange, 581
isothermal reactor design, 193–194
molar flow rates, 236–237
mole balance, 25–26
multiple reactions, 326
nonisothermal reactor design
steady-state, 513
unsteady-state, 637–638
rate data collection and analysis, 273–274
rate laws and stoichiometry, 96–97
Promoters, 412
Propagation step in chain reactions, 348
Propane, dehydrogenation for, 221
Propylene
adsorption of, 432–433
from cumene, 5
in Langmuir–Hinshelwood kinetics, 431–432
Propylene glycol production
in adiabatic reactors, 549–554, 605–608
in CSTR unsteady-state operation, 620–624
Propylene oxide, propylene glycol from, 549–554
Prostaglandin, inhibiting production of, 364
Protease hydrolyzes, 349
Prothrombin, 307
Pseudo-steady-state-hypothesis (PSSH), 339
for active intermediates, 341–345
for epidemiology, 399–400
rate laws derived from, 445
Pursley, J. A., 266
Pyridine hydro-chloride, 251
Q
Q term in CSTRs with heat effects, 546–548
Quarderer, G. C., 271
Questions and problems, 26, 66, 95, 131, 194, 237, 274, 326, 396, 468, 513, 583, 639
active intermediates, enzymatic reactions, pharmacokinetic models, and bioreactors, 396–406
catalysts, 468–473
conversion and reactor sizing, 66–71
flow reactors with heat exchange, 583–598
isothermal reactor design, 194–206
molar flow rates, 237–243
mole balances, 26–31
multiple reactions, 326–337
nonisothermal reactors
steady-state, 513–519
unsteady-state, 639–644
rate data collection and analysis, 274–281
rate laws, 97–102
stoichiometry, 133–138
R
Radioactive decay, 74
Raney nickel, 411
Rate constant
adsorption, 422
Rate data collection and analysis, 245
batch reactor data, 248–249
differential method, 253–259
integral method, 249–253
nonlinear regression, 259–264
data analysis algorithm, 246–247
differential reactors, 264–271
DVD-ROM material, 273–274
experimental planning in, 271
questions and problems for, 274–281
summary, 272–273
supplementary reading, 281
Rate laws, 73
acetic anhydride production, 538
adiabatic equilibrium temperature, 503
adsorption, 422
azomethane decomposition, 342
batch reactors, 145–146, 254–259, 299
butane isomerization, 496, 531
catalytic reactions, 431–434
deducing, 448–449
derived from PSSH, 445
evaluating, 450–452
temperature dependence of, 446
cell growth, 376–378, 381, 383
CSTRs
with cooling coils, 554
liquid phase, 312
multiple reactions, 568–569
series reactions, 303–304
single, 152–153
unsteady-state operation, 621
cumene decomposition, 440
CVD, 459
definitions, 74–76
DVD-ROM material for, 96–97
elementary, 76–79
ethyl acetate saponification, 617
ethylene glycol production, 149, 151, 158
ethylene hydrogenation to ethane, 462
ethylene oxide production, 184
glucose-to-ethanol fermentation, 386
homogeneous reactions, 248
inhibition
competitive, 365
noncompetitive, 368
substrate, 370
uncompetitive, 367
irreversible surface-reaction-limited, 445
isothermal reactor design, 169–170, 209
kinetic, 80–82
MCMT production, 632
methane production, 268–271
methyl bromide production, 230
multiple reactions, 288, 318, 321, 568–569, 626
nitroaniline production, 610
nitrogen oxide production, 214
nonelementary. See Nonelementary rate laws
nonlinear regression for, 262–263
PBR gas phase reactions, 308–309, 528
PFR reactors
complex reactions, 570–571
with heat effects, 528, 570–571
parallel, 565
volume for first-order gas-phase reaction, 142–143
propylene glycol production, 551, 606, 621
from PSSH, 445
questions and problems for, 97–102
rate data analysis, 246–247
and reaction order, 76–86
reactor sizing and design, 93–94
semibatch reactors, 227, 230, 314, 626
steady-state nonisothermal reactor design, 478
sulfur dioxide, 123–125
summary, 95–96
supplementary reading for, 103
surface-reaction-limited irreversible isomerization, 446
surface reactions in catalysts, 426–427
temperature dependence of, 446
toluene hydrodemethylation, 448, 450, 453, 456
triphenyl methyl chloride-methanol reaction, 255–256
trityl-methanol reaction, 253
tubular reactors
adiabatic, 494
for urea
decomposition, 360
removal, 352–353
variable volumetric flow rate, 128–129
web sites for, 673
Rate-limiting
benzene, 439–440
in catalytic reactions, 428–430
cumene adsorption, 434–437
surface reactions, 437–438
Rate of change of energy with time, 657
Rate of desorption, 428
Rate of detachment in adsorption, 422
Rate of disappearance of substrate, 354–355
Rate of formation
in azomethane decomposition, 342
in relative rates of reaction, 74–76
for species, 7–9
Rate of generation, 8–9
Rate of reaction, 4–8
azomethane decomposition, 342
catalysts in diffusion, 415
CSTRs, 13
methane production, 267
multiple reactions, 286
nonlinear regression for, 260
relative, 74–76
Rate of removal in membrane reactors, 220
Rate of transport in membrane reactors, 220
Rate selectivity parameter in parallel reactions, 290
Reactants and reactant concentrations
continuous-flow reactors, 41
in conversion, 34
desired products for, 289–295
differential reactors, 264
energy of formation of, 88
multiple reactions, 285
parallel reactions, 289–295
semibatch reactors, 233
Reaction coordinates, 87
Reaction mechanisms, searching for, 345–348
Reaction order, 76–86
Reaction rate constant, 76, 86–93
Reaction steps with catalysts, 415–416
Reaction surface area in heterogeneous reactions, 7
Reaction time, batch reactors, 144–151
Reaction yields in multiple reactions, 286
Reactions
heterogeneous, 82–83
homogeneous, 80–82
rates. See Rate of reaction
reversible, 83–86
temperature effects on, 92–93
Reactive distillation, 226
Reactor design for toluene hydrodemethylation, 453–455
Reactor lab
isothermal reactor design, 193
rate data collection, 273, 275
Reactor staging with interstate cooling or heating, 505–509
Reactor volume
butane isomerization, 57
continuous-flow reactors, 41–42
conversion factors, 656
ideal gases, 655
membrane reactors, 219
in space time, 61
tubular reactors, 164
Reactors. See also specific reactor types by name
cells as, 28
in parallel reactions, 295–298
in rate data analysis, 246
in series, 49–50
CSTRs, 50–54
CSTRs and PFRs combination, 55–59
CSTRs and PFRs comparisons, 59–60
PFRs, 54
sizing. See Conversion and reactor sizing
Ready-to-eat cereals, 238–239
Reciprocal concentrations, 250
Recycle reactors, 194
Recycle stream in parallel reactions, 295
Reflective learners, 683–684
Reforming catalysts, 441–445
Reforming process, 442
Regression
in activation energy determinations, 91
batch reactor data analysis, 259–264
cell growth, 383
ethylene hydrogenation to ethane, 462–463
methane production, 270–271
Michaelis–Menten equation, 359
toluene hydrodemethylation, 451–452
triphenyl methyl chloride-methanol reaction, 258
Relative rates of reaction
batch reactor series reactions, 299
CSTR liquid phase, 312
MCMT production, 632
multiple reactions, 288
parallel reactions, 565
PBR gas phase reactions, 309
PFR complex reactions with heat effects, 571
stoichiometric coefficients for, 74–76
Removal rate in membrane reactors, 220
Residence-time distributions (RTDs), 212
Reversible gas-phase decompositions, 125–130
Reversible isomerization, 446
Reversible reactions, 74, 83–86
Rhizobium trifollic, 378
Ribonucleic acid (RNA), 373
Ribosomes, 373
RTDs (Residence-time distributions), 212
Runaway reactions
batch: ammonium nitrate, 585, 641
batch reactors with interrupted isothermal operation, 608–615
in PFRs, 582
ortho-nitrochlorobenzene case study, 608–615
SAChE materials, 578–579
T2 explosion case study, 628–635
S
Saccharomyces cerevisiae, 385–387
SAChE (Safety and Chemical Engineering Education) program, 578–579
Safety, 577–579
ammonium nitrate reactor explosion, 585, 641
ethylene glycol, 162
exothermic reactions, 577–579, 608–615
T2 Laboratories, 628–635
ortho-nitrochlorobenzene (ONCB), 608–615
Safety and Chemical Engineering Education (SAChE) program, 578–579
Santa Ana winds, 29
Saponification, 111–112
Scale-up of batch reactor data, 144
Scavengers with active intermediaries, 347
Schmitz, R. A., 556
Seafood gumbo, 676–677
Searching
for mechanisms, 345–348
in nonlinear regression, 260–261
Second-order rate laws, 79
Second-order reactions, 77
batch reactor data analysis, 250
CSTR design, 153–154
irreversible, 155
multiple steady states, 559
PBRs, 178–179
Second reactors in interstage cooling, 508–509
Secondary nutrients, 381
Seitz, Nick, 283
Selectivity
CSTRs, 312
liquid-phase reactions, 226–227, 312, 315
membrane reactors for, 225, 316–321
multiple reactions, 285–286, 289, 316–321
parallel reactions, 295
PBR gas phase reactions, 309
PFR complex reactions with heat effects, 572
semibatch reactors, 315
temperature effects on, 293
Trambouze reactions, 291–295
Semibatch reactors, 225–226
energy balance of, 483, 616, 626–627
with heat exchangers, 615–619
liquid phase, 314–316
multiple reactions in, 624–628
unsteady-state operation in, 226–233
Semiconductor fabrication, 279
chemical vapor deposition in, 458–461
overview, 457
Semilog plots, 90–91
Sensing learners, 684
Sensors, microreactors for, 212
Separating variables with pressure drop, 179
Separation systems, economic incentive for, 285
Sequencing of reactors, 59–60
Sequential learners, 683
Series, reactors in, 49–50
combinations, 55–59
CSTRs, 50–54
PFRs, 54
Series reactions, 283–284
batch reactors, 298–302
blood clotting, 306–307
Seveso accidental release, 579
Shaft work in energy balance, 480
Shuler, M. L., 373–374
Silicon dioxide for microelectronic devices, 279, 457
Simplifications
rate data analysis, 246
triphenyl methyl chloride-methanol reaction, 255
Simpson’s one-third rule, 653
Simpson’s three-eighths rule, 653
Simpson’s three-point formula, 58
Single-site mechanisms
rate-limiting in, 437–438, 445
surface reactions in, 426, 445
Site balance in adsorption isotherms, 421
Sizing reactors. See Conversion and reactor sizing
Small molecule synthesis, 373
Small-scale operations, 10
Smog formation, 28–29
Soap, saponification for, 111–112
Socrates, 1
Sodium bicarbonate, ethylene glycol from, 239
Sodium hydroxide in saponification, 111
Sodium in MCMT production, 629
Sodium thiosulfate, 556
Software packages. See also specific software packages by name
AspenTech, 670
COMSOL, 671
instructions, 671
Polymath, 669–670
Solar energy
biochar gasification, 335–336
biomass production (algae), 404–405
in water splitting, 472–473
solar chemical, 99–100
solar thermal, 334–335
Solid catalysts in PBRs, 18
Solvents from ethylene oxide, 183
Space time, 60–61
Space velocity, 62–63
Spaghetti, cooking, 196
Spartan program, 341
Specialty chemicals, 212
Species, 4–5
mole balances on, 8–9
and variable volumetric flow rate, 115–117
Specific rate of product formation, 379, 381–382
Specific reaction rate, 76, 86–93
Spectroscopic measurements, 445
Spherical bacteria growth, 374
Spherical reactors, 193
Squares of difference, 261
Stability rates
CSTR unsteady-state operation, 620
propylene glycol production, 623
Standard temperature and pressure (STP) in space velocity, 62
Starch, hydrolysis of, 401–402
Startup of CSTRs, 620–624
Stationary phase
substrate balance in, 385
Steady-state bifurcation, 582
Steady state in CSTRs, 13
Steady-state molar flow rates, 486–488
Steady-state nonisothermal reactors, 477
adiabatic operation. See Adiabatic operations
DVD-ROM material, 512–513
energy balance. See Energy balances
equilibrium conversion. See Equilibrium conversions
with heat exchange. See Flow reactors
information required for, 478–479
questions and problems, 513–519
summary, 511–512
supplementary reading, 519
Stern–Volmer Equation, 346–348
Stirred reactors
CSTRs. See Continuous-stirred tank reactors (CSTRs)
unsteady-state operation of
overview, 225–226
semibatch reactors, 226–233
Stoichiometric coefficients
in conversion, 34
in relative rates of reaction, 74–75
acetic anhydride production, 538
adiabatic equilibrium temperature, 503–504
batch systems, 107–113, 145–146
butane isomerization, 496, 531
cell growth, 379–383
CSTRs
with cooling coils, 554
single, 152–153
DVD-ROM material, 132–133
ethyl acetate saponification, 617
ethylene glycol production, 149, 158–159
ethylene oxide production, 184
flow systems, 113–130
glucose-to-ethanol fermentation, 386
isothermal reactors, 209
liquid phase, 314
MCMT production, 632
membrane reactors, 222–223, 318–319
multiple reactions, 288, 318–319, 626
nitroaniline production, 610
nitrogen oxide production, 215
parallel reactions, 565–566
PBR gas phase, 310
PFRs
with heat effects, 528–529, 565–566, 572
reactor volume, 142–143
propylene glycol production, 551, 606, 621
questions and problems, 133–138
steady-state nonisothermal reactors, 478
summary, 131–132
supplementary reading, 137
toluene hydrodemethylation reactors, 453–454, 456
triphenyl methyl chloride-methanol reaction, 256
tubular reactors
adiabatic, 494
STP (standard temperature and pressure) in space
velocity, 62
Streptomyces aureofaciens, 390–391
Stuart Prower factor, 307
Styrene from ethylbenzene, 220–221
Subscripts, 666
Substrates
and dilution rate, 390
disappearance, 354–355, 384–385
enzyme-substrate complex, 349–351
inhibition by, 366, 368, 370–371
mass balances, 384–385
in Michaelis–Menten equation, 354–355, 360
microelectronic fabrication, 457
multiple systems, 395
Sulfunation reactions, 316
Sulfur dioxide
gas-phase reactions, 120–123
oxidation, 582
rate law, 123–125
Sulfuric acid
DDT production, 6
ethylene glycol production, 189–190
Professional Reference Shelf for, 582
Summary Notes, xxi
Sums of squares
ethylene hydrogenation to ethane, 463
multiple reaction analysis, 321
nonlinear regression, 260, 264
Superficial mass velocity, 183
Supplementary reading
active intermediates, enzymatic reactions, pharmacokinetic models, and bioreactors, 406–407
catalysts, 475–476
conversion and reactor sizing, 71
flow reactors with heat exchange, 598–599
isothermal reactor design, 206
molar flow rates, 243
mole balances, 31
multiple reactions, 337–338
nonisothermal reactors
steady-state, 519
unsteady-state, 644–645
rate data collection and analysis, 281
rate laws, 103
stoichiometry, 137
Supported catalysts, 412
Surface area
in membrane reactors, 220
in microreactors, 212
Surface-catalyzed reactions, 212
Surface-reaction-limited operations
cumene decomposition, 440
irreversible isomerization, 446
irreversible rate laws, 445
Surface reactions
in catalysts, 426–428
microelectronic fabrication, 457
rate-limiting, 437–438
in toluene hydrodemethylation, 449–450
Surfactants from ethylene oxide, 183
Switch grass, 334–335
Synthesizing chemical plant design, 188–190
System volume in mole balance equation, 8
Szent-Gyorgyi, Albert, 521
T
T2 Laboratories explosion, 578, 628–635
Tarzlon, 329–330
Tau, space time, 60–61
Taylor, H. S., 413
Taylor series for energy balance, 547
TBA (butyl alcohol), 468–469
Temperature, 477. See also Heat effects
and activation energy, 92–93
in adsorption, 422
in cell growth, 378
conversion factors for, 656
in CSTRs, 13
in enzymatic reactions, 362
in flow reactors with variable volumetric flow rate, 116
nonisothermal reactors
steady-state. See Steady-state nonisothermal reactors
unsteady-state. See Unsteady-state nonisothermal reactors
selectivity affected by, 293
Temperature-concentration phase planes, 620
Tenebrionid beetles, 101
Terephthalic acid (TPA), 331
Termination step in chain reactions, 348
Termolecular reactions, 74
Tessier equation, 377–378
Testing new processes, batch reactors for, 10
Thermal decomposition of isopropyl isocyanate, 279–280
Thermodynamic equilibrium constant, 83, 659–664
Thermodynamically limited reactions, 217
Thermodynamics
equilibrium conversion from, 504
first law of, 479–480
in reversible reactions, 86
Third-order reactions, 77
Three-eighths rule, 653
Three-point rule, 653
Thrombin in blood clotting, 307
Time
in batch reactors, 146–147
concentration, 248
reactant, 35–36
in energy rate change, 657
in growth rates, 378
Time function in semibatch reactors, 228
Time order of magnitude in batch systems, 146
Tissue factor in blood clotting, 306–307
Titanium dioxide, 473–474
TOF (turnover frequency), 413
Toluene
hydrodemethylation of, 82, 446–456
from methylcyclohexane, 474
para-xylene from, 411
Total collective mass, 5
Total concentrations in flow reactors, 121
Total cycle time in batch systems, 147
Total energy in first law of thermodynamics, 479
Total enzyme concentration, 352–353
Total mass, 5
Total molar flow rate
flow reactors, 115–116
gas phase, 210
Total volume
CSTRs in series, 53–54
PFRs in series, 54
Toxic intermediates, 212
TPA (terephthalic acid), 331
Trains of reactors with interstage heating, 518
Trambouze reactions, 291–295
Transfer, mass, 212
Transferases enzymes, 351
Transition state theory, 97
Transition states and energy barriers, 88
Transport
with catalysts, 415
in membrane reactors, 220, 222, 318
Trapezoidal rule, 652
Triethanolamine formation, 284
Triphenyl methyl chloride, 255–259
Trityl-methanol reaction, 251–253
Troubleshooting
corrosion, 98–99
isothermal reactors, 196–197
Truman, Harry S, 477
Tubes
in microreactors, 212
in pressure drop, 183
designing, 162–165
ethylene production, 165–168
gas-phase reactions, 14, 163–165
hemoglobin deoxygenation in, 275
plug-flow. See Plug-flow reactors (PFRs)
space time in, 61
Turbulent flow in packed bed pressure drop, 176
Turnover frequency (TOF), 413
Turnover number in Michaelis–Menten equation, 354
Two-point rule, 652
Tyrosinase, 349–350
U
Ultraformers, 193
Ultrasonic waves, light from, 346–348
Unbound enzyme concentration, 352
Uncompetitive inhibition, 367–368
Underground wet oxidation problem, 675
Undesired products in multiple reactions, 285–286
Uniform surfaces, adsorption in, 425
Unimolecular reactions, 74
Units conversion factors, 656–657
Unstable steady-state temperatures, 561–562
Unsteady-state nonisothermal reactors, 601
batch reactors
adiabatic operation, 605–608
with interrupted isothermal operation, 608–615
DVD-ROM material, 637–638
mole balances, 603
multiple reactions, 624–635
questions and problems, 639–644
semibatch reactors, 615–619
summary, 635–637
Unsteady-state operation of stirred reactors, 225–233, 620–624
Unsupported catalysts, 412
Unwanted products in parallel reactions, 295–297
Urea removal, 352–353
batch reactor calculations for, 359–361
Michaelis–Menten equation for, 354–359
Urease, 352–354
V
Vacant sites in cumene adsorption, 436
Valves in microreactors, 212
Van de Vusse kinetics, 326, 336–337
Vanadium oxides, 473
Vanadium triisopropoxide (VTIPO), 473
Van’t Hoff’s equation, 660
Vapor-phase reactions, irreversible endothermic, 515–516
Variable heat capacities, 513
Variable temperature in energy balance, 484
Variable volume in gas phase flow systems, 115
Variable volumetric flow rate, 115–130
Variance in ethylene hydrogenation to ethane, 463–464
Vat reactors. See Continuous-stirred tank reactors (CSTRs)
Vejtasa, S. A., 556
Velocity, space, 62–63
Verbal learners, 684
Vermont Safety Information Resources, Inc. (Vermont SERI), 162
Vibrational energy, 340
Vinyl allyl ether, 3
Viscosity conversion factors, 656
Visual Encyclopedia of Equipment, 26
Visual learners, 684
Volume. See Reactor volume
Volumetric feed rate in chemostats, 388
Volumetric flow, 114
differential reactors, 265
ethylene oxide production, 186
methane production, 267
tubular reactors, 165
variable, 115–130
VTIPO (vanadium triisopropoxide), 473
W
Wafer fabrication, 279
chemical vapor deposition in, 458–461
overview, 457
Wash-out in cell growth, 389–391
Washington, Booker T., 73
Water
light from, 346–348
splitting, 472–473
Water-gas shift reaction, 662–663
Watson, K. M., 429
Web sites for rate law data, 673
Weighted least squares analysis, 274
Wet oxidation problem, 675
Wetlands module, 236
Wine-making, 377–378
Wooden, John, 33
Work conversion factors, 656
Work term in energy balance, 480–482
Y
Yeasts, 401
doubling times, 378
growth of, 374
Yields
in bioconversions, 372
in multiple reactions, 286
series reactions in batch reactors, 301
YouTube videos, xxi, 195
Z
Zeolite catalysts, 411
Zero-order reactions, 77, 249–250
Zewail, Ahmed, 341